WO2017073287A1 - Polymère séquencé, son procédé de production et son utilisation - Google Patents
Polymère séquencé, son procédé de production et son utilisation Download PDFInfo
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- WO2017073287A1 WO2017073287A1 PCT/JP2016/079852 JP2016079852W WO2017073287A1 WO 2017073287 A1 WO2017073287 A1 WO 2017073287A1 JP 2016079852 W JP2016079852 W JP 2016079852W WO 2017073287 A1 WO2017073287 A1 WO 2017073287A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- the present specification relates to a block copolymer and a method for producing the same, and more particularly to a block copolymer useful as an elastomer having excellent heat resistance, oil resistance and moldability, and a method for producing the same.
- This application is based on Japanese Patent Application No. 2015-210708 filed on October 27, 2015 and Japanese Patent Application No. 2016-108516 filed on May 31, 2016. All of which are hereby incorporated by reference into this application.
- elastomers such as nitrile rubber, acrylic rubber, silicone rubber, fluororubber, and tetrafluoroethylene resin (PTFE) are used as industrially widely used sealing materials.
- acrylic rubber is a rubber-like elastic body mainly composed of acrylic acid ester, and is excellent in heat resistance and oil resistance. Therefore, various hose materials, adhesives, coatings as well as packing and sealing materials for automobiles are used. It is widely used as a material such as wood.
- the engine compartment tends to become hot due to the increase in engine output and the installation of soundproofing materials for the purpose of quietness, and there is a demand for improved heat resistance and oil resistance to elastomers. It is growing.
- Patent Document 1 discloses a specific graft copolymer comprising an epoxy group-containing acrylic rubber (component (A)), a thermoplastic polyester resin (component (B)), and an olefin polymer segment and a vinyl copolymer segment.
- a thermoplastic elastomer composition obtained by crosslinking the above component (A), which is a composition comprising a polymer or a precursor thereof (component (C)) is disclosed.
- Patent Document 2 discloses an acrylic rubber composition obtained by mixing a carboxyl group-containing acrylic rubber with at least one filler and a foil-like filler.
- the compositions described in Patent Documents 1 and 2 are not sufficiently satisfactory for applications requiring high heat resistance and oil resistance. Furthermore, there were also concerns about fluidity and moldability.
- Patent Document 3 includes (A) (meth) acrylic copolymer, (B) transesterification catalyst, (C) thermoplastic resin as essential components, and the above (meth) acrylic copolymer includes (a) A thermoplastic elastomer composition comprising a methacrylic polymer block and a block copolymer (E) containing (b) an acrylic polymer block is disclosed.
- Patent Document 4 discloses a block copolymer containing at least one methacrylic copolymer block (A) and an acrylic copolymer block (B), and a methacrylic copolymer ( A) is a random copolymer block containing a repeating unit derived from a methacrylate monomer and a repeating unit derived from two types of N-substituted maleimide monomers, and the acrylic copolymer block (B) is An acrylic thermoplastic resin containing a repeating unit derived from an acrylate monomer is disclosed.
- thermoplastic elastomer composition described in Patent Document 3 may not be sufficiently satisfied in terms of heat resistance and oil resistance depending on applications, and further improvement in performance is required.
- the thermoplastic resin described in Patent Document 4 exhibits good heat resistance and oil resistance, and can withstand use under severe conditions from the viewpoint of heat resistance and oil resistance.
- there is still room for improvement in terms of fluidity and moldability As described above, an elastomer composition exhibiting high heat resistance and oil resistance and excellent moldability has not yet been shown.
- members such as O-rings and gaskets are strongly required to have a property of recovering deformation when the force is released after applying a force over a long period of time. It has been demanded.
- the technology disclosed in this specification has been made in view of such circumstances. That is, it is an object of the present invention to provide an elastomer material having excellent heat resistance and oil resistance, good fluidity, and excellent moldability, and a method for producing the same. Furthermore, another object of the technology disclosed in the present specification is to provide an elastomer material having a low compression set.
- the polymer block (A) has a structural unit derived from a maleimide compound with respect to all structural units of the polymer block (A) in an amount of 30% by mass to 99% by mass, and has a glass transition temperature (Tg).
- Tg glass transition temperature
- the acrylic polymer block (B) is a block copolymer which is a polymer having a solubility parameter (SP value) of 9.9 or more and Tg of 20 ° C. or less.
- Ph represents a phenyl group
- R 2 represents hydrogen, a hydroxy group, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, or a halogen.
- [5] The block copolymer according to any one of [1] to [4], wherein the polymer block (A) further has a structural unit derived from an amide group-containing vinyl compound.
- [6] The block copolymer according to any one of [1] to [5], wherein at least one of the polymer block (A) and the acrylic polymer block (B) has a crosslinkable functional group.
- the crosslinkable functional group is derived from a crosslinkable monomer, and the structural unit derived from the crosslinkable monomer is 0.01% with respect to all the structural units of the polymer block (A).
- the polymer block (A) has 30 to 99 mass% of structural units derived from a maleimide compound with respect to all the structural units of the polymer block (A), and has a Tg of 150 ° C. or more.
- a polymer, The acrylic polymer block (B) is a polymer having a solubility parameter (SP value) of 9.9 or more and Tg of 20 ° C. or less.
- the third polymerization step includes a step of polymerizing a monomer containing 1% by mass to 70% by mass of styrenes and 30% by mass to 99% by mass of the maleimide compound to obtain the block (A).
- an elastomer material that exhibits extremely high heat resistance and oil resistance can be obtained. Moreover, since it has favorable fluidity
- (meth) acryl means acryl and methacryl
- (meth) acrylate means acrylate and methacrylate
- the “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.
- the block copolymer disclosed in the present specification has one or more polymer blocks (A) containing structural units derived from styrenes and maleimide compounds, and one or more acrylic polymer blocks (B).
- the structure of each block may be the same or different.
- the polymer block (A) has structural units derived from styrenes and maleimide compounds.
- the styrenes include styrene and its derivatives. Specific compounds include styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m- Ethyl styrene, p-ethyl styrene, pn-butyl styrene, p-isobutyl styrene, pt-butyl styrene, o-methoxy styrene, m-methoxy styrene,
- styrene By polymerizing a monomer containing styrenes, a structural unit derived from styrenes can be introduced into the polymer block (A).
- styrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene are preferable from the viewpoint of polymerizability.
- ⁇ -methylstyrene, ⁇ -methylstyrene, and vinylnaphthalene are preferable in that the Tg of the polymer block (A) can be increased and a block polymer having excellent heat resistance can be obtained.
- the proportion of the structural units derived from the styrenes is preferably 1% by mass or more and 70% by mass or less with respect to all the structural units of the polymer block (A). More preferably, they are 5 mass% or more and 70 mass% or less, More preferably, they are 10 mass% or more and 70 mass% or less, More preferably, they are 20 mass% or more and 60 mass% or less. Further, for example, it may be 20% by mass or more and 40% by mass or less. If the structural unit derived from styrene is 1% by mass or more, a block copolymer having excellent moldability can be obtained. On the other hand, if it is 70 mass% or less, since it becomes possible to ensure the required amount of the structural unit derived from the maleimide compound mentioned later, the block copolymer excellent in heat resistance and oil resistance can be obtained.
- the maleimide compounds include maleimide and N-substituted maleimide compounds.
- N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide N-alkyl substituted maleimide compounds such as N-pentylmaleimide, N-hexylmaleimide, N-heptylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide, etc.
- N-cycloalkyl substituted maleimide compounds N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acetylphenyl) maleimide, N- (4-methoxyphenyl) maleimide, N- (4- N-aryl-substituted maleimide compounds such as toxiphenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N-benzylmaleimide, etc., and one or two of them The above can be used.
- a structural unit derived from the maleimide compound can be introduced into the polymer block (A).
- the compound represented by the following general formula (1) is preferable in that the resulting block copolymer is more excellent in oil resistance.
- R 1 represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or PhR 2 .
- Ph represents a phenyl group
- R 2 represents hydrogen, a hydroxy group, an alkoxy group having 1 to 2 carbon atoms, an acetyl group, or a halogen.
- the proportion of the structural unit derived from the maleimide compound is 30% by mass or more and 99% by mass or less with respect to all the structural units of the polymer block (A).
- they are 30 to 95 mass%, More preferably, they are 30 to 90 mass%, More preferably, they are 40 to 80 mass%.
- it may be 50% by mass or more, and for example, may be 60% by mass or more.
- it may be 75% by mass or less, and for example, 70% by mass or less.
- it may be 50% by mass or more and 75% by mass or less, or 60% by mass or more and 70% by mass or less.
- the resulting block copolymer may not have sufficient heat resistance and oil resistance.
- the structural unit derived from the styrenes may be insufficient, resulting in insufficient fluidity and moldability.
- the polymer block (A) contains a crosslinkable functional group
- the crosslinkable functional group may be introduced by using, for example, styrenes and / or maleimide compounds having a functional group such as a hydroxy group, or by copolymerizing a vinyl compound having a crosslinkable functional group.
- vinyl compounds having a crosslinkable functional group unsaturated carboxylic acid, unsaturated acid anhydride, hydroxy group-containing vinyl compound, epoxy group-containing vinyl compound, primary or secondary amino group-containing vinyl compound, reactive silicon group-containing Compounds and the like. These compounds may be used alone or in combination of two or more.
- unsaturated carboxylic acids include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, cinnamic acid, and monoalkyl esters of unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid). Acid, citraconic acid, maleic anhydride, itaconic anhydride, monoalkyl esters such as citraconic anhydride) and the like. These compounds may be used alone or in combination of two or more.
- unsaturated acid anhydride examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds may be used alone or in combination of two or more.
- Hydroxy group-containing vinyl compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth ) 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, and mono (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. These compounds may be used alone or in combination of two or more.
- epoxy group-containing vinyl compound examples include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
- Examples of primary or secondary amino group-containing vinyl compounds include amino groups such as aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N-ethylaminoethyl (meth) acrylate. Containing (meth) acrylic acid ester; amino group-containing (meth) acrylamide such as aminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N-ethylaminoethyl (meth) acrylamide, etc. Etc.
- reactive silicon group-containing compounds include vinyl silanes such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl dimethyl methoxy silane; trimethyoxysilylpropyl (meth) acrylate, Silyl group-containing (meth) acrylic esters such as ethoxysilylpropyl, methyldimethoxysilylpropyl (meth) acrylate, dimethylmethoxysilylpropyl (meth) acrylate; silyl group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether; Examples thereof include silyl group-containing vinyl esters such as vinyl methoxysilylundecanoate. These compounds may be used alone or in combination of two or more.
- an oxazoline group or an isocyanate group can be introduced as a crosslinkable functional group by copolymerizing an oxazoline group-containing monomer or an isocyanate group-containing monomer.
- the polyfunctional polymerizable monomer is a compound having two or more polymerizable functional groups such as a (meth) acryloyl group and an alkenyl group in the molecule, a polyfunctional (meth) acrylate compound, a polyfunctional alkenyl compound, The compound etc. which have both (meth) acryloyl group and an alkenyl group are mentioned.
- allyl (meth) acrylate isopropenyl (meth) acrylate, butenyl (meth) acrylate, pentenyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, etc.
- a compound having both a (meth) acryloyl group and an alkenyl group in the molecule there is a difference in the reactivity of the polymerizable unsaturated group, so that the polymer block (A) is effectively polymerizable unsaturated.
- a group can be introduced.
- These compounds may be used alone or in combination of two or more.
- the amount of the crosslinkable functional group introduced is preferably 0.01 mol% or more based on the total structural unit of the polymer block (A), and more Preferably it is 0.1 mol% or more, More preferably, it is 1.0 mol% or more, Most preferably, it is 2.0 mol% or more.
- the amount of the crosslinkable functional group introduced is 0.01 mol% or more, it is easy to obtain a block copolymer having a small compression set value.
- the upper limit of the amount of the crosslinkable functional group introduced is preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 20 mol% or less, Preferably it is 10 mol% or less.
- the amount of the crosslinkable functional group introduced can be in the range of 0.01 mol% to 60 mol%, preferably 0.1 mol% to 40 mol, based on the total structural units of the polymer block (A). % Or less, and more preferably 1.0 mol% or more and 20 mol% or less.
- the polymer block (A) may have structural units derived from other monomers copolymerizable with these monomers in addition to the above monomer units, as long as the effects of the present disclosure are not impaired. Good.
- examples of other monomers include (meth) acrylic acid alkyl ester compounds, (meth) acrylic acid alkoxyalkyl ester compounds, amide group-containing vinyl compounds, and the like. These compounds may be used alone or in combination of two or more. Among these, an amide group-containing vinyl compound is preferable because a block copolymer having more excellent oil resistance can be obtained.
- the proportion of the structural units derived from the other monomers is in the range of 0% by mass to 50% by mass with respect to all the structural units of the polymer block (A). It is preferable. More preferably, they are 5 mass% or more and 45 mass% or less, More preferably, they are 10 mass% or more and 40 mass% or less.
- (meth) acrylic acid alkyl ester compound examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid n.
- Examples of (meth) acrylic acid alkoxyalkyl ester compounds include methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and (meth) acrylic acid n.
- n-butoxyethyl (meth) acrylate methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, n-propoxypropyl (meth) acrylate, n-butoxypropyl (meth) acrylate
- Examples include methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, n-propoxybutyl (meth) acrylate, and n-butoxybutyl (meth) acrylate.
- amide group-containing vinyl compounds include (meth) acrylamide, tert-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide.
- N, N-dimethylaminopropyl (meth) acrylamide and (meth) acrylamide derivatives such as (meth) acryloylmorpholine
- N-vinylamide series such as N-vinylacetamide, N-vinylformamide and N-vinylisobutyramide Examples include masses.
- monomers other than the above include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
- the glass transition temperature (Tg) of the polymer constituting the polymer block (A) is preferably 150 ° C. or higher. Since Tg can contribute to heat resistance, it may be, for example, 170 ° C. or higher, 180 ° C. or higher, 190 ° C. or higher, or 200 ° C. or higher. Furthermore, it may be 210 ° C. or higher, 220 ° C. or higher, or 230 ° C. or higher. When Tg is less than 150 ° C., the resulting block copolymer may have insufficient heat resistance and oil resistance.
- the upper limit of Tg is 350 ° C. due to the limitation of the constituent monomer units that can be used. Tg may be, for example, 280 ° C.
- Tg can be obtained by differential scanning calorimetry (DSC) as described in Examples described later. Moreover, it can also obtain
- the solubility parameter (SP value) of the polymer block (A) is 10.0 or more, it is preferable in that the oil resistance of the block copolymer becomes better.
- the SP value is more preferably 11.0 or more, further preferably 12.0 or more, and still more preferably 13.0 or more.
- the upper limit of the SP value of the polymer block (A) is not particularly limited, but is usually 30 or less.
- the SP value may be 20.0 or less, and may be 18.0 or less, for example.
- the acrylic polymer block (B) can be obtained by polymerizing a monomer containing an acrylic monomer.
- An acrylic monomer refers to an unsaturated compound having an acryloyl group such as acrylic acid and an acrylic ester compound.
- Acrylic acid ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-acrylic acid 2- Alkyl acrylate compounds such as ethylhexyl, octyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate; Aliphatic cyclic ester compounds of acrylic acid such as cyclohexyl acrylate, methyl cyclohexyl acrylate, tert-butyl cyclohexyl acrylate, cyclododecyl acrylate; Methoxymethyl acrylate, ethoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, n
- an acrylate compound having a functional group such as an amide group, an amino group, a carboxy group, or a hydroxy group may be used.
- an alkyl acrylate ester compound having an alkyl group having 1 to 12 carbon atoms or an alkoxyalkyl group having 2 to 8 carbon atoms is preferable in that a block copolymer having excellent flexibility can be obtained.
- the acrylic monomer contains an alkyl acrylate ester compound having an alkyl group having 1 to 3 carbon atoms or an alkoxyalkyl group having 2 to 3 carbon atoms. It is more preferable.
- the proportion of the structural unit derived from the acrylic monomer is in the range of 20% by mass to 100% by mass with respect to all the structural units of the acrylic polymer block (B). More preferably, it is 50 mass% or more and 100 mass% or less, More preferably, it is 80 mass% or more and 100 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less.
- the structural unit derived from the acrylic monomer when the structural unit derived from the acrylic monomer is in the above range, a good block copolymer tends to be obtained in terms of mechanical properties.
- the acrylic polymer block (B) can use monomers other than the acrylic monomers as constituent monomer units.
- monomers other than acrylic monomers monomers having unsaturated groups other than acryloyl groups can be used, methacryloyl group-containing compounds such as methacrylic acid esters, alkyl vinyl esters, alkyl vinyl ethers and Examples thereof include aliphatic or aromatic vinyl compounds such as styrenes.
- the Tg of the polymer constituting the acrylic polymer block (B) is preferably 20 ° C. or less.
- Tg is preferably 0 ° C. or lower, and more preferably ⁇ 10 ° C. or lower.
- the lower limit of Tg is ⁇ 80 ° C. due to the limitation of constituent monomer units that can be used.
- Tg is ⁇ 20 ° C. or lower, it is preferable in terms of ensuring flexibility even in a low temperature environment. In consideration of cold resistance, it is more preferably ⁇ 30 ° C. or less, and further preferably ⁇ 40 ° C. or less.
- SP value of an acrylic polymer block (B) is 9.9 or more, it is preferable at the point from which the oil resistance of a block copolymer becomes better.
- the SP value is more preferably 10.0 or more, still more preferably 10.1 or more, and particularly preferably 10.2 or more.
- the upper limit of the SP value of the acrylic polymer block (B) is not particularly limited, but is usually 20 or less.
- the polymer block (B) may contain a crosslinkable functional group, which is preferable in that it is easy to obtain a block copolymer having high oil resistance.
- the crosslinkable functional group can be introduced, for example, by copolymerizing a vinyl compound having a crosslinkable functional group.
- vinyl compounds having a crosslinkable functional group unsaturated carboxylic acid, unsaturated acid anhydride, hydroxy group-containing vinyl compound, epoxy group-containing vinyl compound, primary or secondary amino group-containing vinyl compound, reactive silicon group-containing Compounds and the like. These compounds may be used alone or in combination of two or more.
- the amount of the crosslinkable functional group introduced is preferably 0.01 mol% or more based on the total structural unit of the polymer block (B), and more Preferably it is 0.1 mol% or more, More preferably, it is 0.5 mol% or more.
- the amount of the crosslinkable functional group introduced is 0.01 mol% or more, it becomes easy to obtain a block copolymer having high oil resistance.
- the upper limit of the amount of the crosslinkable functional group introduced is preferably 20 mol% or less, more preferably 10 mol% or less, and further preferably 5 mol% or less.
- the amount of the crosslinkable functional group introduced can be in the range of 0.01 mol% or more and 20 mol% or less, preferably 0.1 mol% or more and 10 mol based on the total structural unit of the polymer block (B). % Or less, and more preferably 0.5 mol% or more and 5 mol% or less.
- the block copolymer of the present disclosure has one or more of the polymer block (A) and the acrylic polymer block (B).
- the structure of each block may be the same or different.
- A- (BA) such as an ABA triblock copolymer comprising a polymer block (A) -acrylic polymer block (B) -polymer block (A) in that good performance can be obtained as an elastomer material.
- Those having an n-type structure are preferred.
- the polymer block (A) acts as a hard segment
- the acrylic polymer block (B) acts as a soft segment.
- the block copolymer of the present disclosure exhibits performances excellent in mechanical properties such as elongation at break and strength at break, and becomes a material useful as an elastomer. 10 mass% or more and 60 mass% or less are preferable, and, as for the ratio of the polymer block (A) in a block copolymer, 20 mass% or more and 50 mass% or less are more preferable.
- the proportion of the acrylic polymer block (B) in the block copolymer is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less.
- the SP value of the polymer block (A) and the SP value of the acrylic polymer block (B) preferably have a difference of 0.1 or more.
- the SP values are different from each other by 0.1 or more, in the block copolymer, the two are appropriately phase-separated, so that it is possible to exhibit performance excellent in mechanical strength.
- the difference in SP value is more preferably 0.3 or more, further preferably 0.5 or more, still more preferably 0.8 or more, and particularly preferably 1.0 or more. .
- the difference in SP value is preferably 10 or less, and more preferably 5.0 or less.
- the polymer block (A) has a crosslinkable functional group
- an elastomer material having a smaller compression set value can be obtained by crosslinking using this.
- the cross-linking may be due to a reaction between cross-linkable functional groups introduced into the polymer block (A), or as described later, a cross-linking agent having a functional group capable of reacting with the cross-linkable functional group is added. You may go.
- the reaction between the crosslinkable functional groups introduced into the polymer block (A) when a reactive silicon group is used as the crosslinkable functional group, the polymerization reaction for producing the block copolymer and the subsequent crosslinking reaction are efficiently performed. Can be done automatically.
- the number average molecular weight (Mn) of the block copolymer of the present disclosure is preferably in the range of 10,000 to 500,000. If the number average molecular weight is 10,000 or more, sufficient strength as an elastomer material can be exhibited. Moreover, if it is 500,000 or less, favorable moldability can be ensured.
- the number average molecular weight is more preferably in the range of 20,000 to 400,000, and still more preferably in the range of 50,000 to 200,000.
- the molecular weight distribution (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) value of the block copolymer by the value of the number average molecular weight (Mn) is 1.5 or less in terms of moldability. Preferably there is. More preferably, it is 1.4 or less, More preferably, it is 1.3 or less, More preferably, it is 1.2 or less.
- the lower limit of the molecular weight distribution is 1.0.
- the block copolymer of the present disclosure is not particularly limited as long as the block copolymer having the polymer block (A) and the acrylic polymer block (B) is obtained. Can be adopted. Examples thereof include a method using various controlled polymerization methods such as living radical polymerization and living anion polymerization, a method of coupling polymers having functional groups, and the like. Among these, the living radical polymerization method is preferable because the operation is simple and the method can be applied to a wide range of monomers.
- Living radical polymerization may employ any process such as a batch process, a semi-batch process, a dry continuous polymerization process, and a continuous stirred tank process (CSTR).
- the polymerization method can be applied to various modes such as bulk polymerization without using a solvent, solvent-based solution polymerization, aqueous emulsion polymerization, miniemulsion polymerization or suspension polymerization.
- RAFT method reversible addition-cleavage chain transfer polymerization method
- NMP method nitroxy radical method
- ATRP method atom transfer radical polymerization method
- organic tellurium compounds Various polymerization methods such as polymerization method using TERP (TERP method), polymerization method using organic antimony compound (SBRP method), polymerization method using organic bismuth compound (BIRP method), and iodine transfer polymerization method can be employed.
- TERP method polymerization method using organic antimony compound
- BIRP method organic bismuth compound
- iodine transfer polymerization method can be employed.
- the RAFT method, the NMP method, and the ATRP method are preferable from the viewpoints of controllability of polymerization and ease of implementation.
- RAFT agent a specific polymerization control agent
- RAFT agent various known RAFT agents such as a dithioester compound, a xanthate compound, a trithiocarbonate compound, and a dithiocarbamate compound can be used.
- RAFT agent a monofunctional agent having only one active site may be used, or a bifunctional or more functional agent may be used.
- a bifunctional RAFT agent is preferably used from the viewpoint of efficiently obtaining the block copolymer having the A- (BA) n type structure.
- the usage-amount of a RAFT agent is suitably adjusted with the monomer to be used, the kind of RAFT agent, etc.
- radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used.
- An azo compound is preferred because side reactions are unlikely to occur.
- Specific examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), and the like.
- the radical polymerization initiator may be used alone or in combination of two or more.
- the proportion of the radical polymerization initiator used is not particularly limited, but from the viewpoint of obtaining a polymer having a smaller molecular weight distribution, the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is preferably 0.5 mol or less. More preferably, it is 2 mol or less. From the viewpoint of stably performing the polymerization reaction, the lower limit of the amount of the radical polymerization initiator used relative to 1 mol of the RAFT agent is 0.01 mol. Therefore, the amount of radical polymerization initiator used per 1 mol of RAFT agent is preferably in the range of 0.01 mol to 0.5 mol, and more preferably in the range of 0.05 mol to 0.2 mol.
- the reaction temperature in the polymerization reaction by the RAFT method is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 45 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower. If reaction temperature is 40 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if reaction temperature is 100 degrees C or less, while being able to suppress a side reaction, the restrictions regarding the initiator and solvent which can be used are eased.
- a specific alkoxyamine compound having nitroxide or the like is used as a living radical polymerization initiator, and polymerization proceeds via a nitroxide radical derived therefrom.
- the type of nitroxide radical to be used is not particularly limited, but from the viewpoint of polymerization controllability when polymerizing an acrylate-containing monomer, a compound represented by the general formula (2) is used as the nitroxide compound. Is preferred.
- R 1 is an alkyl group having 1 to 2 carbon atoms or a hydrogen atom
- R 2 is an alkyl group having 1 to 2 carbon atoms or a nitrile group
- R 3 is — (CH 2 ) m—, m Is 0 to 2
- R 4 and R 5 are each an alkyl group having 1 to 4 carbon atoms.
- the nitroxide compound represented by the general formula (2) is primarily dissociated by heating at about 70 to 80 ° C., and causes an addition reaction with the vinyl monomer.
- a polyfunctional polymerization precursor by adding a nitroxide compound to a vinyl monomer having two or more vinyl groups.
- the vinyl monomer can be living polymerized by secondary dissociation of the polymerization precursor under heating.
- the polymerization precursor since the polymerization precursor has two or more active sites in the molecule, a polymer having a narrower molecular weight distribution can be obtained.
- a bifunctional polymerization precursor having two active sites in the molecule it is preferable to use a bifunctional polymerization precursor having two active sites in the molecule.
- the usage-amount of a nitroxide compound is suitably adjusted with the kind etc. of the monomer to be used and a nitroxide compound.
- the block copolymer of the present disclosure is produced by the NMP method, 0.001 to 0.2 mol of the nitroxide radical represented by the general formula (3) with respect to 1 mol of the nitroxide compound represented by the general formula (2).
- the polymerization may be carried out by adding in the range of. ⁇ Wherein R 4 and R 5 are each an alkyl group having 1 to 4 carbon atoms. ⁇
- Addition of 0.001 mol or more of the nitroxide radical represented by the general formula (3) shortens the time for the concentration of the nitroxide radical to reach a steady state. As a result, the polymerization can be controlled to a higher degree, and a polymer with a narrower molecular weight distribution can be obtained. On the other hand, if the amount of the nitroxide radical added is too large, the polymerization may not proceed.
- a more preferable addition amount of the nitroxide radical to 1 mol of the nitroxide compound is in the range of 0.01 to 0.5 mol, and a more preferable addition amount is in the range of 0.05 to 0.2 mol.
- the reaction temperature in the NMP method is preferably 50 ° C. or higher and 140 ° C. or lower, more preferably 60 ° C. or higher and 130 ° C. or lower, still more preferably 70 ° C. or higher and 120 ° C. or lower, particularly preferably 80 ° C. or higher and 120 ° C. or lower. It is as follows. If reaction temperature is 50 degreeC or more, a polymerization reaction can be advanced smoothly. On the other hand, if the reaction temperature is 140 ° C. or lower, side reactions such as radical chain transfer tend to be suppressed.
- a polymerization reaction is generally performed using an organic halide as an initiator and a transition metal complex as a catalyst.
- an organic halide as an initiator, a monofunctional one or a bifunctional or higher one may be used.
- a bifunctional compound is preferably used from the viewpoint of efficiently obtaining the block copolymer having the A- (BA) n type structure.
- bromide and chloride are preferable as the kind of halogen.
- the reaction temperature in the ATRP method is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 50 ° C. or higher and 150 ° C. or lower. If reaction temperature is 20 degreeC or more, a polymerization reaction can be advanced smoothly.
- An A- (BA) n type structure such as an ABA triblock copolymer comprising a polymer block (A) -acrylic polymer block (B) -polymer block (A) is obtained by a living radical polymerization method.
- the target block copolymer may be obtained by sequentially polymerizing each block.
- a polymer block (A) is obtained by polymerizing a monomer containing 1% by mass to 70% by mass of styrene and 30% by mass to 99% by mass of a maleimide compound.
- an acrylic monomer is polymerized to obtain an acrylic polymer block (B).
- an ABA triblock copolymer is obtained by polymerizing a monomer containing 1% by mass to 70% by mass of styrene and 30% by mass to 99% by mass of the maleimide compound. Can do.
- a higher order block copolymer such as a tetrablock copolymer can be obtained.
- it manufactures by the method containing the two-stage polymerization process shown below since a target object is obtained more efficiently, it is preferable.
- an acrylic monomer is polymerized to obtain an acrylic polymer block (B), and then as a second polymerization step, 1% by mass to 70% by mass of styrenes and a maleimide compound A polymer block (A) is obtained by polymerizing a monomer containing 30% by mass to 99% by mass.
- an ABA triblock copolymer comprising a polymer block (A) -acrylic polymer block (B) -polymer block (A) can be obtained.
- a process can be simplified compared with the case where each block is polymerized in sequence.
- higher order block copolymers such as a tetrablock copolymer, can be obtained by repeating said 1st polymerization process and 2nd polymerization process.
- the polymerization of the block copolymer may be performed in the presence of a chain transfer agent, if necessary, regardless of the polymerization method.
- a chain transfer agent known ones can be used. Specifically, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 1-hexanethiol, 2-hexane Thiol, 2-methylheptane-2-thiol, 2-butylbutane-1-thiol, 1,1-dimethyl-1-pentanethiol, 1-octanethiol, 2-octanethiol, 1-decanethiol, 3-decanethiol, 1-undecanethiol, 1-dodecanethiol, 2-dodecanethiol, 1-tridecanethiol, 1-tetradecanethiol, 3-methyl-3-undecanethiol, 5-ethy
- a known polymerization solvent can be used in living radical polymerization.
- aromatic compounds such as benzene, toluene, xylene and anisole
- ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
- ketone compounds such as acetone and methyl ethyl ketone
- dimethylformamide, acetonitrile, dimethyl sulfoxide Examples include alcohol and water.
- the block copolymer of the present disclosure can be used alone or as an elastomer material, but may be in the form of a composition containing known additives or the like as necessary.
- a crosslinkable functional group in at least one of the polymer block (A) and the acrylic polymer block (B)
- a crosslinker capable of reacting with the functional group and crosslinking promotion It is preferable in that an elastomer having a small compression set value can be obtained by blending an agent and the like, and performing a heat treatment as necessary.
- the block copolymer of the present disclosure includes a structural unit derived from a crosslinkable monomer having a carboxyl group, a polyvalent amine, a polyfunctional isocyanate, or the like is preferably used as the crosslinking agent.
- polyvalent amine examples include aliphatic diamine compounds such as hexamethylene diamine, hexamethylene diamine carbamate, and N, N'-dicinnamylidene-1,6-hexane diamine; alicyclic such as 4,4'-methylenebiscyclohexylamine carbamate Diamine compounds: 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4 '-(m-phenylenediisopropylidene) dianiline, 4,4'-(p-phenylenediene) Isopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, 1,3,5 -Benzyltriamine, 1,3,5-benzenetria
- guanidine compounds such as 1,3-di-o-tolylguanidine and 1,3-diphenylguanidine; imidazole compounds such as 2-methylimidazole and 2-phenylimidazole; phosphoric acid, carbonic acid, bicarbonate , Salts of weak acids such as alkali metal salts (Li, Na, K) of acids such as stearic acid and lauric acid; thirds such as triethylenediamine, 1,8-diazabicyclo- [5.4.0] undecene-7 Tertiary amines; Tertiary phosphine compounds such as triphenylphosphine and tri (methyl) phenylphosphine; It is preferable to use together.
- imidazole compounds such as 2-methylimidazole and 2-phenylimidazole
- phosphoric acid, carbonic acid, bicarbonate Salts of weak acids such as alkali metal salts (Li, Na, K) of acids such as stearic acid and
- the crosslinking agent includes an organic carboxylic acid ammonium salt, a dithiocarbamate, a polyvalent carboxylic acid, or an anhydride.
- a combination with a quaternary ammonium salt or a phosphonium salt is preferably used.
- the organic carboxylic acid ammonium salt include ammonium benzoate.
- the dithiocarbamate include zinc salts such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid, and dibenzyldithiocarbamic acid, iron salts, tellurium salts, and the like.
- polyvalent carboxylic acid examples include malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, citric acid, tartaric acid, and phthalic acid.
- quaternary ammonium salt examples include tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, n-dodecyltrimethylammonium bromide, octadecyltrimethylammonium bromide and the like.
- Examples of the phosphonium salt include triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium iodide, triethylbenzylphosphonium chloride, tetrabutylphosphonium bromide and the like.
- a polyfunctional isocyanate or the like is preferably used as the crosslinking agent.
- a polyfunctional isocyanate and a polyfunctional glycidyl compound are preferably used as the crosslinking agent.
- a dithiol compound such as 1,2-ethanedithiol, 1,4-butanethiol, 1,10-decanethiol, 1,4-benzenethiol
- an ene-thiol reaction with a polyvalent thiol such as a trithiol compound such as ethane-1,1,1-trithiol or 1,3,5-benzenetrithiol
- a crosslinking reaction is caused by moisture, so that it is not necessary to add a crosslinking agent or the like.
- additives include plasticizers, oils, anti-aging agents, inorganic fillers, pigments, antioxidants, and ultraviolet absorbers.
- the amount of the additive is preferably 0% by mass or more and 10% by mass or less, more preferably 0% by mass or more and 5% by mass or less, and further preferably 0% by mass or more and 2% by mass with respect to the block copolymer. It is below mass%.
- thermoplastic resin may be added for the purpose of adjusting the performance or processability of the elastomer composition containing the block copolymer of the present disclosure.
- thermoactive resin include polyolefin resins such as polyethylene and polypropylene, polystyrene styrene resins, vinyl resins such as polyvinyl chloride, polyester resins, and polyamide resins. Further, other elastomers may be added and mixed.
- the elastomer composition containing the block copolymer of the present disclosure exhibits good fluidity when heated to about 200 ° C. or more and 250 ° C. or less. For this reason, it can be applied to molding processing by various methods such as extrusion molding, injection molding, and casting molding.
- composition ratio of polymer> The composition ratio of the obtained polymer was identified and calculated from 1 H-NMR measurement.
- Tg Glass transition temperature
- the glass transition temperature (Tg) of the obtained polymer was determined from the intersection of the base line of the heat flux curve obtained using a differential scanning calorimeter and the tangent at the inflection point.
- the heat flux curve shows that about 10 mg of a sample was cooled to ⁇ 50 ° C. and held for 5 minutes, then heated to 300 ° C. at 10 ° C./min, subsequently cooled to ⁇ 50 ° C. and held for 5 minutes, then 10 ° C. / It was obtained under conditions where the temperature was raised to 350 ° C. in min.
- Measuring instrument DSC6220 manufactured by SII Nano Technology Measurement atmosphere: under nitrogen atmosphere.
- Inflection points corresponding to the polymer block (A) and the polymer block (B) by performing differential scanning calorimetry of the block copolymers obtained in the examples and comparative examples. From these, the Tg of each polymer block can be determined.
- ⁇ Initial tensile properties 100 parts of a block copolymer and 0.3 parts of Irganox 1010 (manufactured by BASF) as an antioxidant were dissolved in tetrahydrofuran (THF) to prepare a solution having a polymer concentration of 10%. This was poured into a formwork, and THF was dried and distilled off to prepare a cast film having a thickness of about 1 mm. Using the film obtained above as a sample, the tensile strength at break and elongation at break (25 ° C.) were measured according to JIS K 6251.
- ⁇ Change rate of less than 10%
- ⁇ Change rate of 10% or more (3) Appearance A molded product of 125 mm ⁇ 125 mm ⁇ 2 mm in thickness was injection molded under the following conditions, and the obtained molded product was visually observed based on the following criteria. The appearance was evaluated. ⁇ : No defects such as wrinkles, irregularities, or crisps are observed on the surface.
- X Injection molding machine with defects such as wrinkles, irregularities, or crisps on the surface: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.) Injection molding temperature: 240 ° C Injection pressure: 30% Injection time: 3 sec Mold temperature: 40 °C
- the diameter and thickness of the test piece were 29.0 ⁇ 0.5 mm (diameter) and 12.5 mm ⁇ 0.5 mm (thickness), respectively. It was confirmed that the test piece was sandwiched between compression plates having spacers with a thickness of 9.3 to 9.4 mm. The test piece was held at 70 ° C. for 24 hours under the condition that the ratio of compressing the test piece was 25% by volume, and then the thickness of the central part of the test piece was measured after removing the compression plate at 23 ° C. and leaving it for 30 minutes. The measurement result was applied to the following compression set calculation formula to calculate the compression set (%).
- Compression set (%) (t 0 -t 2) / (t 0 -t 1) ⁇ 100 (Where t 0 is the original thickness (mm) of the test piece, t 1 is the thickness of the spacer (mm), and t 2 is the thickness of the test piece 30 mm after removal from the compression device (mm). Indicates) After compression release, the compression set value when the specimen completely returns to the dimension before compression is 0%, and the dimension shape does not return to its original shape even when released from compression. Since the compression set value in this case is 100%, the smaller the compression set value is between 0% and 100%, the better the recovery.
- ⁇ D hardness> A 2 mm thick film prepared in the same procedure as the above-mentioned compression set is left in a constant temperature and humidity chamber (temperature 23 ° C., relative humidity 50%) for 24 hours or more to stabilize the state, and then three sheets are used.
- the D hardness was measured according to JIS K 7215 “Plastic Durometer Hardness Test Method”.
- the polymer A was obtained by reprecipitation purification from hexane and vacuum drying.
- the molecular weight of the obtained polymer A was Mn69200, Mw75500, and Mw / Mn1.09 from GPC (gel permeation chromatography) measurement (polystyrene conversion).
- Production Examples 2, 6, and 7 (Production of polymers B, F and G) Polymers B, F, and G were obtained in the same manner as in Production Example 1 except that the amounts of DLBTTC, ABN-E, and anisole were as shown in Table 1 and that the reaction time was appropriately adjusted. The molecular weight of each polymer was measured and shown in Table 1.
- Production Example 3 (Production of polymer C) Polymer C was obtained in the same manner as in Production Example 1 except that methyl acrylate was used in place of ethyl acrylate, the charge amount was changed as shown in Table 1, and the reaction time was appropriately adjusted. The molecular weight of the polymer C was measured and shown in Table 1.
- Production Example 4 (Production of polymer D)
- Production Example 8 (Production of polymer H) To a 1 L flask equipped with a stirrer and a thermometer was added 2-methyl-2- [N-tert-butyl-N- (1-diethylphosphono-2,2-dimethylpropyl) -N-oxyl] propionic acid (2.48 g). ), Hexanediol diacrylate (0.72 g), and isopropyl alcohol (20 g) were charged, sufficiently deaerated by nitrogen bubbling, and the reaction was started in a constant temperature bath at 100 ° C. After 1 hour, after cooling to room temperature, the solvent was distilled off under reduced pressure.
- Production Example 10 (Production of polymer J) In place of ethyl acrylate, n-butyl acrylate was used, the amount of charge was changed as shown in Table 1, and the reaction time was appropriately adjusted. Obtained. The molecular weight of the polymer J was measured and shown in Table 1.
- Example 1 (Production of block copolymer 1) In a 1 L flask equipped with a stirrer and a thermometer, the polymer A (87.0 g), ABN-E (0.10 g), N-phenylmaleimide (14.6 g), and styrene (49.8 g) obtained in Production Example 1 were obtained. ) And anisole (342 g) were thoroughly deaerated by nitrogen bubbling, and polymerization was started in a constant temperature bath at 60 ° C. After 3 hours, the reaction was stopped by cooling to room temperature. Block copolymer 1 was obtained by reprecipitation purification from methanol and vacuum drying of the polymerization solution.
- the block copolymer 1 is a triblock copolymer having a structure of polymer block (A) -acrylic polymer block (B) -polymer block (A).
- the block copolymer 1 was evaluated as an elastomer, and the results are shown in Table 8.
- Block copolymers 2 to 24 and 26 were prepared in the same manner as in Example 1 except that the types and amounts of raw materials charged in the flask were changed as shown in Tables 2 to 4 and the reaction time was appropriately adjusted. To 29 were obtained. Molecular weight of each block copolymer, composition ratio of polymer block (A) by 1 H-NMR measurement, and composition ratio of polymer block (A) and acrylic polymer block (B) in the block copolymer are described in Tables 5 to 7.
- the SP value of the polymer block (A) and the acrylic polymer block (B) is determined based on the composition ratio of the polymer block (A) and the composition ratio of the acrylic polymer block (B) by 1 H-NMR measurement.
- Table 5 to 7 are calculated using the above-described calculation formula (Formula 1). Further, based on differential scanning calorimetry of the block copolymers 1 to 24 and 26 to 29, Tg of the polymer block (A) and the acrylic polymer block (B) was determined and listed in Tables 5 to 7.
- Example 25 In a 1 L flask equipped with a stirrer and a thermometer, 2- ⁇ [(2-carboxyethyl) sulfanylthiocarbonyl] sulfanyl ⁇ propanoic acid (0.80 g), ABN-E (0.12 g), N-phenylmaleimide (27. 3 g), styrene (16.4 g) and anisole (89.4 g) were charged, sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 70 ° C.
- the block solution 25 was obtained by reprecipitation purification from methanol and vacuum drying of the polymerization solution.
- Mn86500, Mw124000, and Mw / Mn were 1.43.
- the above-mentioned 2- ⁇ [(2-carboxyethyl) sulfanylthiocarbonyl] sulfanyl ⁇ propanoic acid is a monofunctional RAFT agent, and the resulting polymer is a polymer block (A) -acrylic polymer block (B).
- the SP value of the polymer block (A) was 13.0 and Tg was 210 ° C.
- the SP value of the acrylic polymer block (B) was 10.2 and Tg was ⁇ 20 ° C.
- Examples 1 to 25 correspond to the block copolymer of the present disclosure, and all showed good values of the initial breaking elongation and breaking strength. Further, it was confirmed that even under severe conditions of 150 ° C. and 1000 hours, excellent heat resistance and oil resistance were exhibited. Among them, Examples 9 and 10 using (unsubstituted) maleimide and N-ethylmaleimide as maleimide compounds, and Examples 13 and 10 having a structural unit derived from an amide group-containing vinyl compound in the polymer block (A) and No. 14 showed excellent oil resistance with a very low swelling rate.
- Comparative Example 1 is not sufficient in terms of heat resistance and oil resistance
- Comparative Example 2 is insufficient in terms of oil resistance because there are few structural units derived from the maleimide compound in the polymer block (A). It was.
- the polymer block (A) does not have a structural unit derived from styrenes. The fluidity was not sufficient and the moldability was poor.
- Experimental Examples 1-6 Each raw material was blended as shown in Table 11 to obtain an elastomer composition. However, in Experimental Examples 1 to 4, each raw material component was put into a batch type kneader “Plastograph EC50 type” (manufactured by Brabender) heated to 170 ° C. for the purpose of causing a crosslinking reaction, and 100 rpm / min. The mixture was melt-kneaded for 10 minutes at the rotational speed. The entire kneaded material in a molten state was taken out and cooled at room temperature to obtain an elastomer composition.
- Plastograph EC50 type manufactured by Brabender
- hexamethylenediamine carbamate “Cheminox AC-6” (trade name) manufactured by Unimatex
- zinc dimethyldithiocarbamate “Noxeller PZ”
- dimethyldithiocarbamic acid Futetsu “Noxeller TTFE” (trade name) was used.
- the block copolymer of the present disclosure exhibits good rubber elasticity and is excellent in moldability. For this reason, it can be widely applied in fields such as packing, gaskets, hose materials, etc. for automobile parts, electrical appliances and medical-related products, as well as raw materials for adhesives, members for construction and civil engineering, daily necessities. Moreover, according to the block copolymer of this indication, the elastomer material which exhibits extremely high heat resistance and oil resistance can be obtained. Therefore, among the above, for example, in automotive applications, it is suitably used as a seal material, packing, tube, hose, engine cover, tank cap, etc., particularly as a component in the engine room.
- the elastomer composition containing the block copolymer of the present disclosure is molded and processed into a desired shape, thereby providing automotive parts, home appliance / OA equipment parts, medical equipment parts, packaging materials, civil engineering and building materials, electric wires, It can be suitably used as a material in a wide variety of fields such as sundries.
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Abstract
La présente invention concerne un copolymère séquencé comprenant : une séquence (A) de polymère contenant des motifs structuraux dérivés respectivement d'un composé styrène et d'un composé maléimide ; et une séquence (B) de polymère acrylique. La séquence (A) de polymère est un polymère qui contient un motif structural dérivé d'un composé maléimide en une quantité allant de 30 % en masse à 99 % en masse (inclus), et qui présente une température de transition vitreuse (Tg) supérieure ou égale à 150 °C. La séquence (B) de polymère acrylique est un polymère possédant un paramètre de solubilité (valeur SP) supérieure ou égale à 9,9 et une Tg inférieure ou égale à 20 °C.
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JP2017179154A (ja) * | 2016-03-30 | 2017-10-05 | 株式会社日本触媒 | ブロック共重合体及び樹脂組成物 |
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